Morphology modulation and photo-Fenton degradation of RhB properties in spinel-structured ZnFe2O4 nanocrystals
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摘要: 水资源短缺和人类生产生活需水量的增加使污水净化处理这一话题变热。高级氧化工艺因其高效、环境友好且没有二次污染成为一种行之有效的处理污水方法。其中最具代表性的就是光催化技术和芬顿技术。通过调整工艺参数，采用水热法和煅烧法制备了3种不同形貌的ZnFe2O4纳米晶，即微球状(ZFO-1)、空心球状(ZFO-2)和正六边形状(ZFO-3)。通过XRD、SEM、HRTEM、UV-vis、电化学阻抗谱(EIS)和瞬态光电流响应测试等，对样品的微观结构、形貌、元素组成和光电化学性能进行表征。此外，ZnFe2O4纳米晶光芬顿性能是通过对罗丹明B (RhB)的降解所得出的。结果表明：所制备的3种ZnFe2O4纳米晶均具有立方尖晶石结构和良好的结晶度。ZFO-2表现出优异的可见光吸收能力和最窄的带隙，并发生红移现象。EIS测试表明，ZFO-2的转移内阻最小且瞬态光电流最大，具有优异的光生载流子的迁移和分离能力。ZFO-1、ZFO-2、ZFO-3催化剂的光芬顿降解效率依次为88.2%、97.6%和48.1%，表明具有良好的降解性能。综合得到，ZFO-2具备优异的光降解性能。并探讨了可能的光芬顿降解RhB催化机制。Abstract: The shortage of water resources and the increase of water demand for human production and life have made the topic of wastewater purification and treatment hot. The advanced oxidation process has become a proven method to treat wastewater because it is efficient, environmentally friendly and free of secondary pollution. The most representative ones are photocatalytic technology and Fenton technology. Three different morphologies of ZnFe2O4 nanocrystals, namely microspherical (ZFO-1), hollow spherical (ZFO-2) and orthohexagonal (ZFO-3), were prepared by hydrothermal and calcination methods by adjusting the process parameters. The microstructure, morphology, elemental composition and photoelectrochemical properties of the samples were characterized by XRD, SEM, HRTEM, UV-vis, electrochemical impedance spectroscopy (EIS) and transient photocurrent response tests. Furthermore, the ZnFe2O4 nanocrystal photo-Fenton properties were derived from the degradation of rhodamine B (RhB). The results show that all three prepared ZnFe2O4 nanocrystals have cubic spinel structure and good crystallinity. ZFO-2 exhibits excellent visible light absorption and the narrowest band gap with red-shift phenomenon. EIS tests show that ZFO-2 has the lowest internal resistance to transfer and the highest transient photocurrent, with excellent migration and separation of photogenerated carriers. The photo-Fenton degradation efficiencies of ZFO-1, ZFO-2 and ZFO-3 catalysts are 88.2%, 97.6% and 48.1% in order, indicating good degradation performance. The comprehensive obtained, ZFO-2 has excellent photodegradation performance. And the possible catalytic mechanism of photo-Fenton degradation of RhB was discussed.
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Key words:
- ZnFe2O4 /
- shape control /
- photoelectrochemical properties /
- photo-Fenton /
- dye RhB
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图 1 微球状(ZFO-1)、空心球状(ZFO-2)和正六边形状(ZFO-3) ZnFe2O4纳米晶催化剂的XRD图谱
Figure 1. XRD patterns of microspherical (ZFO-1), hollow spherical (ZFO-2) and orthohexagonal (ZFO-3) ZnFe2O4 nanocrystals catalysts
图 2 ZFO-1 (a)、ZFO-2 (b)和ZFO-3 (c)催化剂的SEM图像
Figure 2. SEM images of ZFO-1 (a), ZFO-2 (b) and ZFO-3 (c) catalysts
图 3 ZFO-2光催化剂的TEM图像(a)和选区电子衍射(SAED)图像(b)
d—Crystal pitch
Figure 3. TEM images (a) and selective electron diffraction (SAED) image (b) of ZFO-2 catalysts
图 5 ZFO-2催化剂的氮吸附-脱附等温线(a)和孔径分布(b)
STP—Standard temperature and pressure
Figure 5. Nitrogen adsorption-desorption isotherm (a) and pore size distribution (b) of ZFO-2 catalysts
图 6 ZFO-1、ZFO-2、ZFO-3样品的紫外-可见光吸收光谱(a)和(αhν)1/2-hν 曲线(b)
a—Original longitudinal intensity; hv—Photon energy and also the transverse coordinate of the absorption spectrum
Figure 6. UV-Vis absorption spectra (a) and (αhν)1/2-hν curves (b) of ZFO-1, ZFO-2 and ZFO-3 samples
图 7 ZFO-2催化剂的Mott-Schottky图
SCE—Standard calomel electrode; C—System momentum
Figure 7. Mott-Schottky diagram of ZFO-2 catalyst
图 8 ZFO-1、ZFO-2、ZFO-3催化剂的电化学阻抗图谱(a)和瞬态光电流响应图谱(b)
Figure 8. Electrochemical impedance profiles (a) and transient photocurrent response profiles (b) of ZFO-1, ZFO-2 and ZFO-3 catalysts
图 9 ZFO-1、ZFO-2、ZFO-3催化剂的光催化(a)和光芬顿(b)降解RhB随时间变化曲线
C0—Pre-light solution concentration; Ct—Post-light solution concentration
Figure 9. Photocatalytic (a) and photo-Fenton (b) degradation of RhB with time for ZFO-1, ZFO-2 and ZFO-3 catalysts
图 10 ZFO-2催化剂的光催化(a)和光芬顿(b)降解RhB随辐照时间变化的UV图谱
Figure 10. Photocatalytic (a) and photo-Fenton (b) UV spectra of ZFO-2 catalysts for the degradation of RhB with irradiation time
图 11 ZnFe2O4光芬顿降解罗丹明B (RhB)的机制示意图
VB—Valence band; CB—Conduction band; Eg—Band-gap energy; NHE—Normal hydrogen electrode
Figure 11. Schematic diagram of the mechanism of rhodamine B (RhB) degradation by ZnFe2O4 photo-Fenton
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